JP6923355B2 - Formation of SiOC thin film - Google Patents

Description

The present disclosure relates generally to the field of semiconductor device manufacturing, and more specifically to the formation of silicon oxycarbide (SiOC) films with desirable chemical resistance.

Increasingly, there is a need for dielectric materials with relatively low dielectric constant (k) values and relatively slow acidic wet etching rates. Silicon Oxycarbide or Silicon Oxycarbonitride (SiOCN) may meet some of these requirements. Generally, the SiOC or SiOCN deposition process requires oxygen plasma. In addition, nitrogen in SiOCN membranes can cause problems during treatment, for example, SiOCN membranes can cause photoresist poisoning.

In some embodiments, a plasma enhanced atomic layer deposition process is provided that forms a silicon oxycarbide (SiOC) thin film on a substrate in the reaction space. In some embodiments, the process or method was generated by a step of bringing the surface of the substrate into contact with a nitrogen-free vapor phase silicon precursor and a plasma formed from a second reactant containing hydrogen. An optional step of contacting the adsorbed silicon species with at least one reaction species, the step of contacting the adsorbed silicon species with oxygen-free step and the step of contacting the adsorbed silicon species until a SiOC film having a desired thickness is formed. It can include at least one deposition cycle, including steps that repeat in.

In some embodiments, the ratio of the wet etch rate of the SiOC thin film to the wet etch rate of the thermal silicon oxide is less than about 5. In some embodiments, the ratio of the wet etch rate of the SiOC thin film to the wet etch rate of the thermal silicon oxide is less than about 0.3. In some embodiments, the ratio of the wet etch rate of the SiOC thin film to the wet etch rate of the thermal silicon oxide is less than about 0.1. In some embodiments, the SiOC thin film is deposited on a three-dimensional structure on the substrate. In some embodiments, the wet etch rate ratio of the wet etch rate of SiOC formed on the upper surface of the three-dimensional structure to the wet etch rate of SiOC formed on the side wall surface of the three-dimensional structure is the diluted HF. It is about 1: 1 in.

In some embodiments, the vapor phase silicon precursor is halogen free. In some embodiments, the vapor phase silicon precursor comprises bis (triethoxysilyl) ethane (BTESE). In some embodiments, the vapor phase silicon precursor comprises 3-methoxypropyltrimethoxysilane (MPTMS). In some embodiments, the vapor phase silicon precursor comprises (3-mercaptopropyl) trimethoxysilane. In some embodiments, the reactive species comprises a hydrogen plasma, a hydrogen atom, a hydrogen radical or a hydrogen ion. In some embodiments, the reactants are generated from a second reactant containing a noble gas. In some embodiments, the second reactant comprises H _2. In some embodiments, the reactants are generated from a second reactant containing less than about 20 atomic% nitrogen. In some embodiments, the second reactant consists essentially of H _2.

In some embodiments, the SiOC thin film contains at least 20 atomic% oxygen. In some embodiments, the SiOC thin film contains at least 0.1 atomic% carbon. In some embodiments, the SiOC thin film contains at least 1 atomic% carbon. In some embodiments, the SiOC thin film contains at least 5 atomic% carbon. In some embodiments, the SiOC thin film contains less than about 10 atomic% nitrogen.

In some embodiments, a method of forming a silicon oxycarbide (SiOC) thin film on a substrate in the reaction space is provided. In some embodiments, such methods can include multiple deposition cycles, wherein at least one deposition cycle comprises a nitrogen-free silicon precursor and at least one reactive species containing hydrogen. It includes a step of alternately and sequentially contacting the surface of the substrate with the reactant of 2. In some embodiments, the deposition cycle is repeated two or more times to form a SiOC thin film.

In some embodiments, at least one reactive species is generated by a plasma formed from an oxygen-free gas. In some embodiments, at least one reactive species is generated by a plasma formed from a nitrogen-free gas. In some embodiments, the silicon precursor has the general formula has a _{^{(R II O) 3 Si-}} R I -Si (OR II) 3, wherein, ^{R I} and ^{R II} is independently selected C _{1 to} C ₅ alkyl ligands. In some embodiments, the silicon precursor comprises BTESE. In some embodiments, the silicon precursor has the general formula _{^{Si (OR I) 4-x}} R II x, where, x is an integer of 0 to 3, ^{R I} is independently selected C _{1 to} C ₇ alkyl ligands to be produced, R ^II is an independently selected ligand consisting of carbon and / or hydrogen and / or oxygen. In some embodiments, the silicon precursor comprises MPTMS. In some embodiments, the silicon precursor has the general formula _{^{(R I O) 4-x}} Si- (R II -O-R III) x, where, x is an integer from 0 to 3 Yes, ^RI and R ^II are independently selected C _{1 to} C ₇ alkyl ligands, respectively, and R ^III is an independently selected ligand consisting of carbon and / or hydrogen and / or oxygen.

In some embodiments, at least one deposition cycle is a PEALD cycle. In some embodiments, the reactants are generated by applying RF power of 5 watts (W) to about 5000 W to the second reactant. In some embodiments, the deposition cycle is carried out at a process temperature of about 100 ° C to about 300 ° C. In some embodiments, the deposition cycle is carried out at a process temperature of less than about 100 ° C. In some embodiments, the substrate comprises an organic material.

In some embodiments, a method of forming a silicon oxycarbide (SiOC) thin film on a substrate in the reaction space is provided. In some embodiments, the method involves contacting the surface of the substrate with a nitrogen-free silicon precursor and exposing the substrate to purge gas and / or vacuum to remove excess silicon precursors and reaction by-products. A step of removing them, if any, and a step of bringing the surface of the substrate into contact with a second reactant containing hydrogen, the second reactant comprising at least one reactant produced by the plasma. The contact with the step and the step of exposing the substrate to purge gas and / or vacuum to remove excess second reactants and reaction by-products, if any, until a SiOC thin film of the desired thickness is formed. It can include a step of repeating the step of causing.

FIG. 5 is a process flow diagram for depositing a silicon oxycarbide (SiOC) thin film by a plasma enhanced atomic layer deposition (PEALD) process according to some embodiments of the present disclosure. It is a figure which shows the molecular structure of the exemplary silicon precursor which concerns on some embodiments. It is a plot of the precursor bottle temperature and the SiOC film growth rate for the SiOC sample film deposited according to some embodiments. SiOC film growth rate as a function of plasma output for the film deposited according to some embodiments, refractive index, and wet etch rate ratio to hot silicon oxide in dHF (0.5 wt%) (WERR: wet to TOX). It is a figure which shows etch rate ratio). It is a figure which shows the SiOC film growth rate and the second reaction gas composition about the film deposited according to some embodiments.

Silicon oxycarbide (SiOC) films have a wide variety of applications, for example, in integrated circuit fabrication, as will be apparent to those skilled in the art. More specifically, SiOC films with slow etching rates have a wide variety of applications both outside the semiconductor industry and outside the semiconductor industry. The SiOC film can be useful as, for example, an etch stop layer, a sacrificial layer, a low-k spacer, an antireflection layer (ARL), and a passivation layer.

According to some embodiments of the present disclosure, various SiOC films, precursors, and methods of depositing said films are provided. In some embodiments, the SiOC film has a relatively slow wet etch rate, for example in dHF.

In some embodiments, the SiOC thin film is deposited on the substrate by a plasma enhanced atomic layer deposition (PEALD) process. In some embodiments, the SiOC thin film is not deposited by the liquid phase method. In some embodiments, the SiOC thin film is deposited on a three-dimensional structure such as fins in the formation of fin-type FET elements.

The formula for the silicon oxycarbide membrane is commonly referred to herein as SiOC for convenience and brevity. As used herein, SiOC is not intended to limit, limit or define the bond or chemical state of any of Si, O, C and / or any other element in the membrane, eg, the oxidation state. No. Further, in some embodiments, the SiOC thin film may contain one or more elements such as S in addition to Si, O and / or C. In some embodiments, the SiOC film can include a Si—C bond and / or a Si—O bond. In some embodiments, the SiOC film can include Si—C and Si—O bonds and may not include Si—N bonds. In some embodiments, the SiOC film can include Si—S bonds in addition to Si—C and / or Si—O bonds. In some embodiments, the SiOC membrane can contain more Si—O bonds than Si—C bonds, eg, a ratio of Si—O bonds to Si—C bonds of about 1: 1 to about. It can be 10: 1. In some embodiments, SiOC can contain from about 0% to about 40% carbon on an atomic basis. In some embodiments, SiOC is about 0.1% to about 40%, about 0.5% to about 30%, about 1% to about 30%, or about 5% to about 20% on an atomic basis. Can contain carbon. In some embodiments, the SiOC membrane can contain from about 0% to about 70% oxygen on an atomic basis. In some embodiments, SiOC can contain from about 10% to about 70%, about 15% to about 50%, or about 20% to about 40% oxygen on an atomic basis. In some embodiments, the SiOC film can contain from about 0% to about 50% silicon on an atomic basis. In some embodiments, SiOC can contain from about 10% to about 50%, about 15% to about 40%, or about 20% to about 35% silicon on an atomic basis. In some embodiments, SiOC is about 0.1% to about 40%, about 0.5% to about 30%, about 1% to about 30%, or about 5% to about 20% on an atomic basis. Can contain sulfur. In some embodiments, the SiOC film may not contain nitrogen. In some other embodiments, the SiOC membrane can contain from about 0% to about 5% nitrogen on an atomic basis (at%).

The ALD-type process is based on a controlled, generally self-limiting surface reaction. Gas phase reactions are generally avoided by alternating sequential contact of the substrate with the reactants. Gas phase reactants are separated from each other in the reaction chamber, for example by removing excess reactants and / or reaction by-products during the reactant pulses. The reactants can be removed from near the substrate surface using purge gas and / or vacuum. In some embodiments, excess reactants and / or reaction by-products are removed from the reaction space by, for example, purging with an inert gas.

In some embodiments, a plasma enhanced ALD (PEALD) process is used to deposit the SiOC film. In some embodiments, the PEALD process described herein does not use oxygen plasma. In some embodiments, the PEALD process described herein does not include reactants including oxygen plasma. In some embodiments, the PEALD process described herein does not use nitrogen plasma. In some embodiments, the PEALD process described herein does not include reactants including nitrogen plasma. In some embodiments, the PEALD process described herein can use hydrogen plasma. In some embodiments, the PEALD process described herein can include reactants including hydrogen plasma. Briefly, the substrate or the object to be treated is placed in a reaction chamber and subjected to alternating and repeated surface reactions. In some embodiments, a thin SiOC film is formed by repeating a self-limiting ALD cycle. In some embodiments, each ALD cycle comprises at least two different steps to form a SiOC film. Contact and removal of the reactant or precursor from the substrate can be considered as one step. In the first step, the first vapor phase reactant or precursor containing silicon comes into contact with the substrate to form about one or less single layer on the surface of the substrate. This reactant is also referred to herein as a "silicon precursor," "silicon-containing precursor," or "silicon reactant," for example, bis (triethoxysilyl) ethane (BTESE) or 3-methoxypropyltrimethoxysilane (. MPTMS). In some embodiments, excess first gas phase reactants and any reaction by-products are removed from near the substrate surface. The first gas phase reactant and any reaction by-product can be removed from near the substrate surface using purge gas and / or vacuum. In some embodiments, excess reactants and / or reaction by-products are removed from the reaction space by, for example, purging with an inert gas. In some embodiments, the substrate can be transferred, for example, by transferring the substrate to a different reaction chamber to facilitate removal of reactants and / or reaction by-products.

In the second step, the second reactant, including the reactants, can come into contact with the substrate and convert the adsorbed silicon species to SiOC. In some embodiments, the second reactant comprises a hydrogen precursor. In some embodiments, the reactive species comprises excited species. In some embodiments, the second reactant comprises a species derived from a hydrogen-containing plasma. In some embodiments, the second reactant comprises hydrogen radicals, hydrogen atoms and / or hydrogen plasma. The second reactant can include another species that is not a hydrogen precursor. In some embodiments, the second reactant is a species derived from a noble gas, such as one or more of He, Ne, Ar, Kr or Xe, eg, as a radical, in the form of a plasma, or of an element. Can be included in form. These noble gas-derived reactive species do not necessarily give the material to the sedimentary membrane, but in some situations they can contribute to membrane growth and help form and ignite the plasma. In some embodiments, the reactive species produced from the noble gas can affect the amount or extent of damage to the underlying substrate. One of ordinary skill in the art can select a noble gas (s) suitable for a particular application. In some embodiments, the gas used to form the plasma can always flow through the deposition process, but can only be activated intermittently. In some embodiments, the gas used to form the plasma is oxygen free. In some embodiments, the adsorbed silicon precursor does not come into contact with the reactive species produced by the plasma from oxygen. In some embodiments, the second reactant, including the reactants, is produced in an oxygen-free gas. For example, in some embodiments, the second reactant can include plasma generated in an oxygen-free gas. In some embodiments, the second reactant is oxygen less than about 50 atomic% (at%), oxygen less than about 30 atomic%, oxygen less than about 10 atomic%, oxygen less than about 5 atomic%. Can be produced in a gas containing less than about 1 atomic% oxygen, less than about 0.1 atomic% oxygen, less than about 0.01 atomic% oxygen, or less than about 0.001 atomic% oxygen.

In some embodiments, the gas used to form the plasma is nitrogen free. In some embodiments, the adsorbed silicon precursor does not come into contact with the reactive species produced by the plasma from nitrogen. In some embodiments, the second reactant, including the reactants, is produced in a nitrogen-free gas. For example, in some embodiments, the second reactant can include plasma generated in a nitrogen-free gas. However, in some embodiments, the gas used to form the plasma can include nitrogen. In some other embodiments, the second reactant can include nitrogen radicals, nitrogen atoms and / or nitrogen plasma. In some embodiments, the second reactant is less than about 25 atomic% (at%) nitrogen, less than about 20 atomic% nitrogen, less than about 15 atomic% nitrogen, less than about 10 atomic% nitrogen. , Nitrogen less than about 5 atomic%, nitrogen less than about 1 atomic%, nitrogen less than about 0.1 atomic%, nitrogen less than about 0.01 atomic%, or gas containing nitrogen less than about 0.001 atomic% Can be generated in. In some embodiments, the second reactant can be produced in a gas containing hydrogen and nitrogen, for example, the second reactant can comprise H ₂ and N ₂ . In some embodiments, the second reactant is produced in a gas in which the ratio of _{N 2} to H _{2 (N 2} / H ₂ ) is less than about 20%, less than about 10%, or less than about 5%. can do.

In some embodiments, the gas used to form the plasma contains neither nitrogen nor oxygen. In some embodiments, the adsorbed silicon precursor does not come into contact with the reactive species produced by the plasma from nitrogen or oxygen. In some embodiments, the second reactant, including the reactants, is produced in a gas that is free of nitrogen and oxygen. For example, in some embodiments, the second reactant can include plasma generated in a gas containing neither nitrogen nor oxygen.

In some embodiments, excess second reactants and any reaction by-products are removed from near the substrate surface. The second reactant and any reaction by-product can be removed from near the substrate surface using purge gas and / or vacuum. In some embodiments, excess reactants and / or reaction by-products are removed from the reaction space by, for example, purging with an inert gas. In some embodiments, the substrate can be moved, for example, by moving the substrate to a different reaction chamber to facilitate removal of reactants and / or reaction by-products.

The composition of the final membrane can be adjusted by adding additional steps and omitting the steps as needed.

One or more kinds of reactants can be supplied by using a carrier gas such as Ar or He. In some embodiments, the silicon precursor and the second reactant are supplied utilizing a carrier gas.

In some embodiments, the two steps may overlap or be combined. For example, the silicon precursor and the second reactant can be brought into contact with the substrate at the same time at a partially or completely overlapping stage. In addition, the order of the stages can be changed, albeit referred to as the first and second stages, and the first and second reactants, and the ALD cycle can be initiated from any one of the stages. That is, unless otherwise stated, the reactants can be brought into contact with the substrate in any order and the process can be initiated from any of the reactants.

As discussed in more detail below, in some embodiments where the SiOC film is deposited, one or more deposition cycles are initiated by contacting the substrate with a silicon precursor followed by a second precursor. .. In another embodiment, deposition can be initiated by contacting the substrate with a second precursor followed by a silicon precursor.

In some embodiments, a substrate to be deposited, such as a semiconductor object to be processed, is carried into a reaction space or a reactor. The reactor can be part of a cluster tool in which various processes are carried out in the formation of integrated circuits. In some embodiments, a flow reactor is utilized. In some embodiments, a showerhead reactor is utilized. In some embodiments, a space-split reactor is utilized. In some embodiments, mass-produced single-wafer ALD reactors are used. In another embodiment, a batch reactor containing multiple substrates is used. For embodiments using a batch ALD reactor, the number of substrates is in the range of 10 to 200, 50 to 150, or 100 to 130.

Examples of suitable reactors that can be used include ASM America, Inc., Phoenix, Arizona. And ASM Europe B. in Almere, the Netherlands. V. F-120® Reactor, F-450® Reactor, Pulsar® Reactor such as Pulsar® 2000, Pulsar® 3000, EmerALD®, available from Commercially available devices such as (trademark) reactors and Advance (registered trademark) 400 series reactors can be mentioned. Other commercially available reactors include ASM Japan K. with trade names Eagle® XP and XP8. Reactors made by K (Tokyo, Japan) can be mentioned.

In some embodiments, the exposed surface of the object to be treated can be pretreated, if desired, to provide a reaction site that reacts with the first step of the ALD process. In some embodiments, no separate pretreatment step is required. In some embodiments, the substrate is pretreated to provide the desired surface termination. In some embodiments, the substrate is pretreated with plasma.

Excess reactants and reaction by-products are removed from the vicinity of the substrate, especially from the substrate surface, during the reactant contact step. In some embodiments, excess reactants and reaction by-products, if present, are removed from the substrate surface by purging the reaction chamber during the reactant contact step, for example purging with an inert gas. Remove. The flow rate and contact time of each reactant are adjustable, the removal steps are similar, and the quality and properties of the membrane can be controlled.

As mentioned above, in some embodiments, the gas is continuously supplied to the reaction chamber during each deposition cycle or during the entire ALD process to generate plasma in the gas in the reaction chamber or upstream of the reaction chamber. Supply the reaction species by. In some embodiments, the gas is nitrogen free. In some embodiments, the gas can include noble gases such as helium, argon and the like. In some embodiments, the gas is helium. In some embodiments, the gas is argon. The fluid gas can also act as a purge gas for the first and / or second reactants (or reactants). For example, the fluidized argon can act as a purge gas for the first silicon precursor and can also act as a second reactant (as a source of reactants). In some embodiments, argon or helium can serve as a source of excited species for converting the purge gas of the first precursor and the silicon precursor to the SiOC membrane. In some embodiments, the gas produced therein by the plasma is nitrogen-free and the adsorbed silicon precursor does not come into contact with the reactive species produced by the plasma from the nitrogen. In some embodiments, the gas produced therein by the plasma is oxygen-free and the adsorbed silicon precursor does not come into contact with the reactive species produced by the plasma from the oxygen. In some embodiments, the gas produced therein by the plasma contains neither oxygen nor nitrogen, and the adsorbed silicon precursor does not come into contact with oxygen or the reactants produced by the plasma from nitrogen.

The cycle is repeated until a film of the desired thickness and composition is obtained. In some embodiments, deposition parameters such as precursor flow rate, contact time, removal time and / or the reactants themselves are one or more deposition cycles during the ALD process to obtain a film with the desired properties. Can be changed at.

In some embodiments, the surface of the substrate is brought into contact with the reactants. In some embodiments, a 1-pulse reactant is fed into the reaction space containing the substrate. The term "pulse" can be understood to include feeding the reactants into the reaction chamber for a predetermined period of time. The term "pulse" does not limit the length or duration of the pulse, and the pulse can be any time. In some embodiments, the substrate is transferred to a reaction space containing the reactants. In some embodiments, the substrate is subsequently transferred from the reaction space containing the first reactant to a second different reaction space containing the second reactant.

In some embodiments, the substrate is first contacted with the silicon reactant. After the initial surface termination, if necessary or desired, the substrate is brought into contact with the first silicon reactant. In some embodiments, a first silicon reactant pulse is supplied to the object to be treated. According to some embodiments, the first reactant pulse comprises a carrier gas stream and volatile silicon species such as BTESE, MPTMS that are susceptible to react with the surface of the object to be treated. Therefore, the silicon reactant is adsorbed on the surface of these objects to be treated. The first reactant pulse self-saturates the surface of the object to be treated with the silicon reactant species so that the excess component of the first reactant pulse does not further react with the molecular layer formed by this process.

The first silicon reactant pulse can be supplied in the form of a gas. Silicon precursor gas is considered "volatile" herein if it exhibits sufficient vapor pressure to transfer the species to the object to be treated at a concentration sufficient to saturate the exposed surface under process conditions. ..

In some embodiments, the silicon reactant is in contact with the surface for about 0.05 seconds to about 5.0 seconds, about 0.1 seconds to about 3 seconds, or about 0.2 seconds to about 1.0 seconds. do. The optimum contact time can be easily determined by those skilled in the art based on the individual circumstances.

After a sufficient amount of time for about one molecular layer to adsorb to the substrate surface, excess first silicon reactants and reaction by-products, if any, are removed from the substrate surface. In some embodiments, removal of excess reactants and reaction by-products, if any, can include purging the reaction chamber. In some embodiments, excess reactants and reaction by-products, if any, of the first reactant, while continuing to flow carrier gas or purge gas for a time sufficient to diffuse or purge them from the reaction space. The reaction chamber can be purged by stopping the flow. In some embodiments, the excess first precursor is purged with an inert gas such as helium, argon flowing throughout the ALD cycle. In some embodiments, the substrate can be transferred from the reaction space containing the first reactant to a second different reaction space. In some embodiments, the first reactant is removed for about 0.1 seconds to about 10 seconds, about 0.3 seconds to about 5 seconds, or about 0.3 seconds to about 1 second. Contact and removal of silicon reactants can be considered as the first or silicon step of the ALD cycle.

In the second step, a second reactant containing a reactive species such as hydrogen plasma is supplied to the object to be treated. Hydrogen plasma can be formed by generating plasma in hydrogen in the reaction chamber or upstream of the reaction chamber, for example, _{by flowing hydrogen (H 2} ) through a remote plasma generator.

In some embodiments, plasma is generated in the fluidized in H ₂ gas. _{In some embodiments, H 2} is supplied to the reaction chamber before the plasma is ignited or before hydrogen atoms or radicals are formed. In some embodiments, H ₂ is continuously fed into the reaction chamber to generate or supply hydrogen-containing plasmas, atoms or radicals as needed.

Generally, the second reactant, including, for example, hydrogen plasma, is brought into contact with the substrate for about 0.1 to about 10 seconds. In some embodiments, a second reactant, such as hydrogen-containing plasma, is applied to the substrate for about 0.1 to about 10 seconds, 0.5 to about 5 seconds, or 0.5 to about 2.0. Contact for seconds. However, depending on the reactor type, substrate type and surface area thereof, the second reactant contact time can be even longer than about 10 seconds. In some embodiments, the contact time can be several minutes. The optimum contact time can be easily determined by those skilled in the art based on the individual circumstances.

In some embodiments, the second reactant is fed in two or more different pulses and no other reactant is introduced between any of the two or more pulses. For example, in some embodiments, plasma, such as hydrogen-containing plasma, is supplied in two or more consecutive pulses and no Si precursor is introduced between the consecutive pulses. In some embodiments, the plasma discharge is supplied for the first time and the plasma discharge is applied for the second time, eg, about 0.1 seconds to about 10 seconds, about 0.5 seconds to about 5 seconds, or about. The plasma is being fed by erasing for 1.0 to about 4.0 seconds and re-exciting it for a third time prior to the introduction of another precursor or removal step, such as before the Si precursor or purge step. Generates two or more consecutive plasma pulses. Additional pulsed plasmas can be introduced as well. In some embodiments, the plasma is ignited at each of the pulses for the same amount of time.

In some embodiments, a plasma, eg, a hydrogen-containing plasma, is generated by applying an RF power of about 5W to about 5000W, 10W to about 2000W, about 50W to about 1000W, or about 200W to about 800W. be able to. In some embodiments, it is possible to make the RF power density of about 0.02 W / cm ² ~ about 2.0 W / cm ^2, or about 0.05 W / cm ² ~ about 1.5 W / cm ^2. RF power can be applied to a second reactant flowing during the plasma contact time, continuously flowing through the reaction chamber, and / or flowing through the remote plasma generator. Therefore, in some embodiments, the plasma is generated in place and in another embodiment the plasma is generated remotely. In some embodiments, a showerhead reactor is utilized to generate plasma between the susceptor (on which the substrate is located) and the showerhead plate. In some embodiments, the distance between the susceptor and the shower head plate is about 0.1 cm to about 20 cm, about 0.5 cm to about 5 cm, or about 0.8 cm to about 3.0 cm.

The previously adsorbed molecular layer of silicon species is completely saturated with the plasma pulse, and after sufficient time to react with the plasma pulse, excess reactants and reaction by-products are removed from the substrate surface.

In some embodiments, removal of excess reactants and reaction by-products, if any, can include purging the reaction chamber. In some embodiments, excess reactants and reaction by-products, if any, of the second reactant, while continuing to flow carrier gas or purge gas for a time sufficient to diffuse or purge them from the reaction space. The reaction chamber can be purged by stopping the flow. In some embodiments, the excess second precursor is purged with an inert gas such as helium, argon flowing throughout the ALD cycle. In some embodiments, the substrate can be transferred from the reaction space containing the second reactant to a different reaction space. Removal can be from about 0.1 seconds to about 10 seconds, from about 0.1 seconds to about 4 seconds, or from about 0.1 seconds to about 0.5 seconds in some embodiments. Overall, the contact and removal of the reactive species is the second reactive species step in the SiOC atomic layer deposition cycle.

The two steps together form one ALD cycle and are repeated to form a SiOC thin film of the desired thickness. Although the ALD cycle is generally referred to herein as starting at the silicon stage, in another embodiment it is contemplated that the cycle can be started at the reactive species stage. One of skill in the art should recognize that the first precursor stage generally reacts with the termination left by the final stage of the previous cycle. Thus, if the reaction species step is the first step in the first ALD cycle, the reactants are probably not pre-adsorbed to the substrate surface and are not present in the reaction space, but in subsequent cycles the reaction species step. Effectively follows the silicon stage. In some embodiments, one or more different ALD cycles are provided in the deposition process.

According to some embodiments of the present disclosure, the PEALD reaction is carried out at a temperature of about 25 ° C. to about 700 ° C., about 50 ° C. to about 600 ° C., about 100 ° C. to about 450 ° C., or about 200 ° C. to about 400 ° C. Can be carried out. In some embodiments, the optimum reactor temperature can be limited by the maximum permissible heat history. Therefore, in some embodiments, the reaction temperature is from about 100 ° C to about 300 ° C. In some applications, the maximum temperature is about 200 ° C., so the PEALD process is carried out at that reaction temperature.

The substrate on which the thin film is deposited can contain various types of materials. In some embodiments, the substrate can include an integrated circuit object to be processed. In some embodiments, the substrate can contain silicon. In some embodiments, the substrate can include silicon oxide, such as thermal oxides. In some embodiments, the substrate can include a high k dielectric material. In some embodiments, the substrate can contain carbon. For example, the substrate can include an amorphous carbon layer, graphene and / or carbon nanotubes.

In some embodiments, the substrate can include metals including, but not limited to, W, Cu, Ni, Co and / or Al. In some embodiments, the substrate can include metal nitrides, including, but not limited to, TiN and / or TaN. In some embodiments, the substrate can include metal carbides, including, but not limited to, TiC and / or TaC. In some embodiments, the substrate can include metallic chalcogenides, including, but not limited to _{, MoS 2} , Sb ₂ Te _{3 and / or GeTe.} In some embodiments, the substrate can include materials that are oxidized by exposure to the oxygen plasma process but not by the PEALD process described herein.

In some embodiments, the substrates used in the PEALD process described herein can include organic materials. For example, the substrate can include organic materials such as plastics, polymers and / or photoresists. In some embodiments where the substrate comprises an organic material, the reaction temperature of the PEALD process can be less than about 200 ° C. In some embodiments, the reaction temperature can be less than about 150 ° C, less than about 100 ° C, less than about 75 ° C, or less than about 50 ° C.

In some embodiments where the substrate contains an organic material, the maximum process temperature can be as low as 100 ° C. In some embodiments where the substrate contains an organic material, the deposition of SiOC thin films on the organic material may be degraded in the deposition process, which would otherwise include the plasma generated from oxygen, in the absence of oxygen-generated plasma. Can be made possible.

According to some embodiments of the present disclosure, the pressure in the reaction chamber during treatment is maintained at about 0.01 Torr to about 50 Torr, or about 0.1 Torr to about 10 Torr. In some embodiments, the pressure in the reaction chamber exceeds about 6 Torr or about 20 Torr. In some embodiments, the SiOC deposition process can be carried out at pressures of about 20 Torr to about 500 Torr, about 20 Torr to about 50 Torr, or about 20 Torr to about 30 Torr.

In some embodiments, the SiOC deposition process can include multiple deposition cycles, with at least one deposition cycle performed in the high pressure region. For example, the deposition cycle of the PEALD process can include alternating sequential contact of the substrate with the silicon precursor and the second reactant under high pressure. In some embodiments, one or more deposition cycles of the PEALD process can be performed at process pressures of about 6 Torr to about 500 Torr, about 6 Torr to about 50 Torr, or about 6 Torr to about 100 Torr. In some embodiments, one or more deposition cycles include process pressures greater than about 20 Torr, including about 20 Torr to about 500 Torr, about 30 Torr to about 500 Torr, about 40 Torr to about 500 Torr, or about 50 Torr to about 500 Torr. Can be carried out at. In some embodiments, one or more deposition cycles are performed at process pressures of about 20 Torr to about 30 Torr, about 20 Torr to about 100 Torr, about 30 Torr to about 100 Torr, about 40 Torr to about 100 Torr, or about 50 Torr to about 100 Torr. can do.

SiOC PEALD
As described above, and as discussed in more detail below, in some embodiments, the SiOC thin film is placed on a substrate in the reaction space by a plasma enhanced atomic layer deposition (PEALD) process. Can be deposited in. According to some embodiments, the SiOC thin film is deposited on a substrate having a three-dimensional shape in a fin-type FET application example or the like by a PEALD process. In some embodiments, the PEALD process described herein can be used for a variety of purposes. For example, the PEALD process described herein can be used to form hardmask layers, sacrificial layers, protective layers or low-k spacers. The PEALD process described herein can be used, for example, in memory device applications.

In some embodiments, by the oxygen plasma-free PEALD process described herein on a substrate that cannot withstand O-plasma without damage, such as a substrate containing an organic and / or photoresist material. A SiOC thin film can be deposited. In some embodiments, the SiOC thin film can be deposited by a PEALD process in which the silicon precursor and the second reactant are nitrogen-free.

With reference to FIG. 1, and according to some embodiments,
In step 120, a step of bringing the substrate into contact with a nitrogen-free vapor-phase silicon-containing precursor so that the silicon species are adsorbed on the surface of the substrate,
In step 130, the step of removing excess silicon-containing precursors and reaction by-products from the substrate surface, if any,
In step 140, the substrate is brought into contact with a second reactant containing a hydrogen-containing reactive species produced by the plasma, thereby converting the adsorbed silicon species to SiOC.
In step 150, the step of removing excess second reactants and reaction by-products, if any, from the substrate surface, and
In step 160, the SiOC thin film is reacted in the reaction space by the PEALD deposition process 100, which comprises at least one cycle including the step of optionally repeating the contact and removal steps to form a SiOC thin film of the desired thickness and composition. Is deposited on the substrate.

In some embodiments, step 140 may include the step of remotely generating or forming a plasma or reaction species prior to contacting the substrate with the second reactant.

According to some embodiments, the SiOC plasma ALD deposition cycle can be used to deposit the SiOC thin film. In one embodiment, a SiOC thin film is formed on the substrate by an ALD-type process involving multiple SiOC deposition cycles. Each SiOC deposition cycle
A step of bringing the substrate into contact with a nitrogen-free vapor-phase silicon reactant so that the silicon compound is adsorbed on the surface of the substrate.
With the step of exposing the substrate to purge gas and / or vacuum,
The step of bringing the substrate into contact with the reactants produced by forming a plasma in a second reactant containing hydrogen,
With the step of exposing the substrate to purge gas and / or vacuum,
It comprises the step of optionally repeating the contact and exposure steps until a SiOC thin film of the desired thickness and composition is obtained.

In some embodiments, the step of exposing the substrate to purge gas and / or vacuum can include the step of continuing the flow of the Inactive Carrier Gas while stopping the flow of the precursor or reactant. .. In some embodiments, the steps of exposing the substrate to purge gas and / or vacuum include stopping the flow of precursor and carrier gas into the reaction chamber and evacuating the reaction chamber, for example by a vacuum pump. Can be included. In some embodiments, the step of exposing the substrate to purge gas and / or vacuum can include the step of transferring the substrate from the first reaction chamber to a second different reaction chamber containing the purge gas. In some embodiments, the step of exposing the substrate to purge gas and / or vacuum can include moving the substrate from the first reaction chamber to a second different reaction chamber under reduced pressure. In some embodiments, the reactive species may be nitrogen-free.

According to some embodiments
The step of bringing the substrate into contact with the BTESE so that the silicon species are adsorbed on the surface of the substrate,
Steps to remove excess BTESE and reaction by-products, if any, from the substrate surface,
A step in which the substrate is brought into contact with a second reactant containing a plasma-generated reactant and the reactant contains hydrogen,
The step of removing excess second reactants and reaction by-products, if any, from the substrate surface,
The SiOC thin film is deposited on the substrate in the reaction space by a PEALD deposition process involving at least one cycle involving the step of optionally repeating the contact and removal steps to form a SiOC thin film of the desired thickness and composition. ..

In some embodiments, the step of contacting the substrate with the second reactant can include the step of remotely generating or forming a plasma or reactant prior to contacting the substrate with the second reactant. .. In some embodiments, the reactive species may be nitrogen-free.

In certain embodiments, a SiOC thin film is formed on the substrate by an ALD-type process involving multiple SiOC deposition cycles, each SiOC deposition cycle containing a nitrogen-free first vapor phase silicon precursor and reactive species. It includes a step of alternately and sequentially bringing the substrates into contact with the reactants of 2. In some embodiments, the silicon precursor can include BTESE and the second reactant can include hydrogen. In some embodiments, the second reaction species may not contain nitrogen. In some embodiments, the second reaction species can contain a relatively small amount of nitrogen, as described above.

According to some embodiments
The step of bringing the substrate into contact with MPTMS so that the silicon species are adsorbed on the surface of the substrate,
Steps to remove excess MPTMS and reaction by-products, if any, from the substrate surface,
A step in which the substrate is brought into contact with a second reactant containing a plasma-generated reactant and the reactant contains hydrogen,
The step of removing excess second reactants and reaction by-products, if any, from the substrate surface,
The SiOC thin film is deposited on the substrate in the reaction space by a PEALD deposition process involving at least one cycle involving the step of optionally repeating the contact and removal steps to form a SiOC thin film of the desired thickness and composition. ..

In some embodiments, the step of contacting the substrate with the second reactant can include the step of remotely generating or forming a plasma or reactant prior to contacting the substrate with the second reactant. .. In some embodiments, the reactive species may be nitrogen-free.

In certain embodiments, a SiOC thin film is formed on the substrate by an ALD-type process involving multiple SiOC deposition cycles, each SiOC deposition cycle containing a nitrogen-free first vapor phase silicon precursor and reactive species. It includes a step of alternately and sequentially bringing the substrates into contact with the reactants of 2. In some embodiments, the silicon precursor can include BTESE and the second reactant can include hydrogen. In some embodiments, the second reaction species may not contain nitrogen. In some embodiments, the second reaction species can contain a relatively small amount of nitrogen, as described above.

According to some embodiments, the SiOC plasma ALD deposition cycle can be used to deposit the SiOC thin film. In one embodiment, a SiOC thin film is formed on the substrate by an ALD-type process involving multiple SiOC deposition cycles. Each SiOC deposition cycle
A step of bringing the substrate into contact with a nitrogen-free vapor-phase silicon reactant so that the silicon compound is adsorbed on the surface of the substrate.
With the step of exposing the substrate to purge gas and / or vacuum,
A step of bringing the substrate into contact with the reactants produced by forming a plasma in a second reactant that contains hydrogen and can also contain nitrogen.
With the step of exposing the substrate to purge gas and / or vacuum,
It comprises the step of optionally repeating the contact and exposure steps until a SiOC thin film of the desired thickness and composition is obtained.

In certain embodiments, a SiOC thin film is formed on the substrate by an ALD-type process involving multiple SiOC deposition cycles, each SiOC deposition cycle containing a nitrogen-free first vapor phase silicon precursor and reactive species. It includes a step of alternately and sequentially bringing the substrates into contact with the reactants of 2.

In some embodiments, the PEALD process is performed at about 100 ° C. to about 650 ° C., about 100 ° C. to about 550 ° C., about 100 ° C. to about 450 ° C., about 200 ° C. to about 600 ° C., or about 200 ° C. to about 400 ° C. Perform at a temperature of ° C. In some embodiments, the temperature is about 300 ° C. In some embodiments, the temperature is about 200 ° C. In some embodiments, for example, if the substrate contains an organic material such as an organic photoresist, the PEALD process can be performed at a temperature below about 100 ° C. In some embodiments, the PEALD process is performed at a temperature below about 75 ° C or less than about 50 ° C. In some embodiments, plasma can be generated by applying RF power to the second reactant. RF power can be applied to the second reactant, thereby producing a reactant. In some embodiments, RF power can be applied to a second reactant flowing continuously through the reaction chamber and / or through a remote plasma generator. Therefore, in some embodiments, the plasma is generated in place and in another embodiment the plasma is generated remotely. In some embodiments, the RF power applied to the second reactant is from about 5W to about 5000W, 10W to about 2000W, about 100W to about 1000W, or about 200W to about 800W. In some embodiments, the RF power applied to the second reactant is about 200 W. In some embodiments, the RF power applied to the second reactant is about 400 W. In some embodiments, the RF power applied to the second reactant is about 800 W.

As discussed in more detail below, in some embodiments where the SiOC membrane is deposited, one or more PEALD deposition cycles are initiated by the supply of a silicon precursor followed by a second reactant. In another embodiment, the deposition can be initiated by feeding a second reactant followed by a silicon precursor. One of skill in the art should recognize that the first precursor stage generally reacts with the termination left by the final stage of the previous cycle. Thus, if the reaction species step is the first step in the first PEALD cycle, the reactants are probably not pre-adsorbed to the substrate surface and are not present in the reaction space, but in subsequent PEALD cycles, the reaction species. The stage effectively follows the silicon stage. In some embodiments, one or more different PEALD subcycles are provided in the process of forming the SiOC thin film.

Si Precursors Several different suitable Si precursors can be used in the PEALD process of the present disclosure. In some embodiments, suitable Si precursors may be nitrogen-free. In some embodiments, suitable Si precursors can include silane.

In some embodiments, a suitable Si precursor can include two Si atoms linked by at least one hydrocarbon group or attached to at least one hydrocarbon group. In some embodiments, a suitable Si precursor can include two Si atoms linked by at least one alkyl group or attached to at least one alkyl group. In some embodiments, a suitable Si precursor can include two Si atoms linked by at least one alkoxy group or attached to at least one alkoxy group. In some embodiments, a suitable Si precursor can include two Si atoms linked by at least one silyl group or attached to at least one silyl group. In some embodiments, a suitable Si precursor can include two Si atoms linked by at least one silyl ether group or attached to at least one silyl ether group. In some embodiments, a suitable Si precursor can contain at least one -SH group, which can be attached to an alkyl chain or silicon atom. In some embodiments, a suitable Si precursor can contain at least one mercapto group. In some embodiments, suitable Si precursor may include at least one -R-SH structure, wherein, R can be a C ₁ -C ₅ alkyl group. In some embodiments, a suitable Si precursor can include at least one -SH group on the alkyl chain and one or more alkoxy groups attached to a silicon atom.

In some embodiments, a suitable Si precursor can include at least one Si atom added or bonded to one or more alkoxy groups. In some embodiments, a suitable Si precursor can include at least one Si atom added or bonded to one or more alkyl groups. In some embodiments, a suitable Si precursor can include at least one Si atom added or bonded to an alkyl group and an alkoxy group.

In some embodiments, at least some Si precursors suitable for depositing SiOC by the PEALD process can include crosslinked alkoxysilanes of the following general formula:

(1) (R ^II O) ₃ Si-R ^I -Si (OR ^II ) ₃

Wherein each of, R ^I and R ^II may be the alkyl groups independently selected. In some embodiments, each of ^{R I} and ^{R II} are _C 1 -C ₅ alkyl ligand selected from methyl, ethyl, n- propyl, isopropyl, tert-butyl, independently of pentyl.

According to some embodiments, some Si precursors can include crosslinked alkoxyalkylsilanes of the following general formula:

^{_{(2) R III y (OR}} II) x Si-R I -Si (OR II) x R III y

Wherein each ^of, R ^{I, R II} and ^{R III} may be an alkyl group selected independently an x + y = 3. In some embodiments, each of ^{R I} and ^{R II} are _C 1 -C ₅ alkyl ligand selected from methyl, ethyl, n- propyl, isopropyl, tert-butyl, independently of pentyl. In some embodiments, R ^III can be an independently selected C _1- C ₈ alkyl ligand.

According to some embodiments, some Si precursors can include cyclic alkoxysilanes of the following general formula:

(3) (R ^II O) ₂ Si-R ^I ₂ -Si (OR ^II ) ₂

Equation (3) can also be expressed by the following structural formula.

Wherein each of, R ^I and R ^II may be the alkyl groups independently selected. In some embodiments, each of ^{R I} and ^{R II} are _C 1 -C ₅ alkyl ligand selected from methyl, ethyl, n- propyl, isopropyl, tert-butyl, independently of pentyl.

According to some embodiments, some Si precursors can include cyclic alkoxyalkylsilanes of the following general formula:

^{_{(4) R III y (OR}} II) x Si-R I 2 -Si (OR II) x R III y

Equation (4) can also be expressed by the following structural formula.

Wherein each ^of, R ^{I, R II} and ^{R III} may be an alkyl group selected independently an x + y = 2. In some embodiments, each of ^{R I} and ^{R II} are _C 1 -C ₅ alkyl ligand selected from methyl, ethyl, n- propyl, isopropyl, tert-butyl, independently of pentyl. In some embodiments, R ^III can be an independently selected C _1- C ₈ alkyl ligand.

According to some embodiments, some Si precursors can include linear alkoxysilanes of the following general formula:

^{_{(5) (R II O)}} 3 Si- (O-Si-R I 2) n -O-Si (OR II) 3

In the formula, ^RI can be an independently selected alkyl group or hydrogen, and R ^II can be an independently selected alkyl group, n = 1-4. In some embodiments, each of ^{R I} and ^{R II} are _C 1 -C ₅ alkyl ligand selected from methyl, ethyl, n- propyl, isopropyl, tert-butyl, independently of pentyl. In some embodiments, R ^I can be a hydrogen, R ^II can be a C ₁ -C ₅ alkyl ligand selected independently.

According to some embodiments, some Si precursors can include linear alkoxysilanes of the following general formula:

^{_{(6) R III y (OR}} II) x Si - (- R I -Si) n -Si (OR II) x R III y

Wherein each ^of, R ^{I, R II} and ^{R III} may be an alkyl group selected independently an x + y = 2, n may be 1 or more. In some embodiments, ^{R I} and ^{R II} are _C 1 -C ₅ alkyl ligand selected from methyl, ethyl, n- propyl, isopropyl, tert-butyl, independently of pentyl. In some embodiments, R ^III can be an independently selected C _1- C ₈ alkyl ligand.

According to some embodiments, some Si precursors can include alkoxysilanes of the following general formula:

_{^{(7) Si (OR I)}} 4

Wherein, R ^I can be an alkyl group independently selected. In some embodiments, ^{R I} can be methyl, ethyl, n- propyl, isopropyl, tert-butyl, and _C 1 -C ₅ alkyl ligand selected independently, such as pentyl.

According to some embodiments, some Si precursors can include alkoxyalkylsilanes of the following general formula:

_{^{(8) Si (OR I)}} 4-x R II x

Wherein each of, ^{R I} and ^{R II} may be the alkyl group selected independently a x = 1 to 3. In some embodiments, ^{R I} can be methyl, ethyl, n- propyl, isopropyl, tert-butyl, and _C 1 -C ₅ alkyl ligand selected independently, such as pentyl. In some embodiments, R ^II can be an independently selected C _1- C ₈ alkyl ligand.

According to some embodiments, some Si precursors can include an alkoxysilane having the following general formula, which does not contain nitrogen.

_{^{(9) Si (OR I)}} 4-x R II x

Wherein, R ^I can be an alkyl group selected independently, R ^II is, carbon, contains hydrogen and / or oxygen, can be any ligand that does not contain nitrogen, x = 1 ~ 3. In some embodiments, ^{R I} can be methyl, ethyl, n- propyl, isopropyl, tert-butyl, and _C 1 -C ₅ alkyl ligand selected independently, such as pentyl. In some embodiments, the R ^II can include, for example, alkenyl, alkynyl, phenyl, carbonyl, aldehyde, ester, ether, carboxyl, peroxy, hydroperoxy, thiol, acrylate or methacrylate ligand.

According to some embodiments, some Si precursors can have the following general formula:

_{^{(10) Si (OR I)}} 4-x R II x

Wherein a x = 0 to 3, ^{R I} can be a _C 1 -C ₇ or _C 1 -C ₅ alkyl ligands are independently ^{selected, R II,} the carbon and / or hydrogen and / Alternatively, it can be an independently selected ligand consisting of oxygen. For example, in some embodiments, R ^II can be an alkoxyalkyl group. In some embodiments, the R ^II can be, for example, an alkenyl, alkynyl, phenyl, carbonyl, aldehyde, ester, ether, carboxyl, peroxy or hydroperoxy group. In some embodiments, for example, ^RI is a methyl group, R ^II is a 3-methoxypropyl ligand, and x is 1.

According to some embodiments, some Si precursors can have the following general formula:

_{^{(11) (R I O)}} 4-x Si- (R II -O-R III) x

Wherein a x = 0 to 3, each of ^{R I} and ^{R II} may be a _C 1 -C ₇ or _C 1 -C ₅ alkyl ligands are independently ^{selected, R III} is carbon and It can be an independently selected ligand consisting of / or hydrogen and / or oxygen. For example, in some embodiments, R ^III can be, for example, an alkenyl, alkynyl, phenyl, carbonyl, aldehyde, ester, ether, carboxyl, peroxy or hydroperoxy group. In some embodiments, for example, ^RI , R ^II and R ^III are independently selected from methyl, ethyl, i-propyl, n-propyl, n-butyl, i-butyl and t-butyl, respectively. Can be the basis.

According to some embodiments, some Si precursors can have the following general formula:

(12) Si ( ^RI ) _4-x-y R ^II _x R ^III _y

Wherein a x + y = 0~4, ^{R I} is an alkoxide ligand, or halide having 1-5 carbon ^{atoms, R II} is any ligand containing ^{sulfur, R III} is It consists of one of the sulfhydryl, sulfide, disulfide, sulfinyl, sulfonyl, sulfino, sulfo, thiocyanate, isothiocyanate or carbonothio oil functional groups. In some embodiments, ^RI , R ^II and R ^III can be selected independently. In some embodiments, the R ^I may include a methoxy ligand, R ^II can contain 3-mercaptopropyl, and x = 1, and y = 0. That is, in some embodiments, some Si precursors can include Si (OCH ₃ ) ₃ C ₃ H ₆ SH. In some embodiments, the Si precursor can include mercaptomethylmethyldiethoxysilane, 3-mercaptopropylmethyldimethoxysilane and / or 3-mercaptopropyltriethoxysilane.

In some embodiments, the silicon precursor is halogen free. In some embodiments, the silicon precursor is nitrogen free. In some embodiments, the carbon chain can be unsaturated and can contain double carbon-carbon bonds. In some other embodiments, the carbon chain can contain atoms other than carbon and hydrogen. According to some embodiments, a suitable silicon precursor can include at least a compound having any of the general formulas (1)-(11). FIG. 2 shows an exemplary molecular structure of suitable Si precursors of the above formulas (1)-(11). In some embodiments, the silicon precursor can include bis (triethoxysilyl) ethane (BTESE). In some embodiments, the silicon precursor can include 3-methoxypropyltrimethoxysilane (MPTMS, i.e. Si (OCH ₃ ) ₃ C ₃ H ₆ OCH ₃ ). In some embodiments, the silicon precursor can include (3-mercaptopropyl) trimethoxysilane.

In some embodiments, more than one silicon precursor can be brought into contact with the substrate surface at the same time during the ALD step. In some embodiments, the silicon precursor can include more than one of the silicon precursors described herein. In some embodiments, the first silicon precursor is used in the first ALD cycle and the second different ALD precursor is used in the subsequent ALD cycle. In some embodiments, multiple silicon precursors can be used during a single ALD step, for example, to optimize certain properties of the deposited SiOC membrane. In some embodiments, only one silicon precursor can be contacted with the substrate during deposition. In some embodiments, only one silicon precursor and one second reactant or composition of the second reactant may be present during the deposition process. In some embodiments, there is no metal precursor during the deposition process. In some embodiments, the silicon precursor is not used as the silylating agent. In some embodiments, the deposition temperature and / or duration of the silicon precursor contact step is selected so that the silicon precursor does not decompose. In some embodiments, the silicon precursor may be degraded during the silicon precursor contact step. In some embodiments, the silicon precursor is free of halogens such as chlorine and fluorine.

Second Reactant As described above, the second reactant for depositing SiOC in accordance with the present disclosure can include a hydrogen precursor that can contain a reactant. In some embodiments, reaction species include, but are not limited to, radicals, plasmas and / or excited atoms or species. Such reaction species can be produced, for example, by plasma discharge, heat rays or another suitable method. In some embodiments, the reaction species can be generated remotely from the reaction chamber, eg, upstream of the reaction chamber (“remote plasma”). In some embodiments, the reaction species can be generated in the reaction chamber in the immediate vicinity of the substrate or directly on the substrate (“direct plasma”).

Suitable plasma compositions for the PEALD process include hydrogen reactive species, i.e. some form of hydrogen plasma, radicals, or atomic hydrogen. In some embodiments, the second reactant can include a reactant, at least partially formed from _{H 2.} In some embodiments, the plasma can also include noble gases such as He, Ne, Ar, Kr and Xe, or Ar or He in the form of plasma, as radicals or in the form of atoms.

In some embodiments, the second reactant can include a reactive species formed from H _2. In some embodiments, the second reactant is hydrogen greater than about 25 atomic% (at%), hydrogen greater than about 50 atomic%, hydrogen greater than about 75 atomic%, hydrogen greater than about 85 atomic%. It can be produced from a gas containing more than about 90 atomic% hydrogen, more than about 95 atomic% hydrogen, about 96 atomic%, 97 atomic%, more than 98 atomic%, or more than about 99 atomic% hydrogen.

In some embodiments, the gas used to generate the reactive species, such as plasma, can consist essentially of hydrogen. Thus, in some embodiments, the second reactant can essentially consist of hydrogen plasma, hydrogen radicals, or atomic hydrogen. In some embodiments, the second reactant is more than about 25 atomic% hydrogen, more than about 50 atomic% hydrogen, 75 atomic%, more than about 85 atomic%, more than about 90 atomic%, about. It can contain more than 95 atomic%, more than about 96 atomic%, 97 atomic%, 98 atomic%, or more than about 99 atomic% hydrogen plasma, hydrogen radicals, or atomic hydrogen. In some embodiments, the second reactant is at least partially, be formed from H ₂ and one or more other gases, H ₂ and other gases (s), It is supplied at a flow rate ratio of about 1: 1000 to about 1000: 1 or more (H ₂ / another gas (s)). In some embodiments, the flow ratio (H ₂ / another gas (s) is greater than about 1: 1000, greater than about 1: 100, greater than about 1:50, about 1:20. More than, more than about 1:10, more than about 1: 6, more than about 1: 3, more than about 1: 1, more than about 3: 1, more than about 6: 1, more than about 10: 1. It can be greater than, greater than about 20: 1, greater than 50: 1, 100: 1, or greater than or equal to 1000: 1.

In some embodiments, the second reactant is free of species produced from oxygen. Therefore, in some embodiments, the reactive species do not form from a gas containing oxygen. In some embodiments, the second reactant, including the reactants, is produced from an oxygen-free gas. For example, in some embodiments, the second reactant can include plasma generated from an oxygen-free gas. In some other embodiments, the second reactant is oxygen less than about 50 atomic% (at%), oxygen less than about 30 atomic%, oxygen less than about 10 atomic%, less than about 5 atomic%. Can be produced from oxygen containing less than about 1 atomic% oxygen, less than about 0.1 atomic% oxygen, less than about 0.01 atomic% oxygen, or less than about 0.001 atomic% oxygen. .. In some embodiments, the second reactant does not contain _{O 2} , H ₂ O or O _3.

In some embodiments, the hydrogen plasma may or may not contain oxygen-containing species (eg, oxygen ions, radicals, atomic oxygen). For example, oxygen-containing gas is not used to generate hydrogen plasma. In some embodiments, the oxygen-containing gas (e.g., O ₂ gas) does not flow into the reaction chamber in the hydrogen plasma step.

In some embodiments, the oxygen-containing gas is not used to generate the hydrogen plasma. In some embodiments, the oxygen-containing gas (e.g., O ₂ gas) does not flow into the reaction chamber in the hydrogen plasma step.

In some embodiments, the second reactant is free of species produced from nitrogen. Therefore, in some embodiments, the reactive species do not form from a nitrogen-containing gas. In some embodiments, the second reactant, including the reactants, is produced from a nitrogen-free gas. For example, in some embodiments, the second reactant can include plasma generated from a nitrogen-free gas. In some embodiments, the second reactant is less than about 25 atomic% (at%) nitrogen, less than about 20 atomic% nitrogen, less than about 15 atomic% nitrogen, less than about 10 atomic% nitrogen. , Nitrogen less than about 5 atomic%, nitrogen less than about 1 atomic%, nitrogen less than about 0.1 atomic%, nitrogen less than about 0.01 atomic%, or gas containing nitrogen less than about 0.001 atomic% Can be generated from. In some embodiments, the second reactant does not contain _{N 2} , NH ₃ or N ₂ H _4.

In some embodiments, the hydrogen plasma may or may not contain nitrogen-containing species (eg, nitrogen ions, radicals, atomic nitrogen). For example, nitrogen-containing gas is not used to generate hydrogen plasma. In some embodiments, the nitrogen-containing gas (eg, N ₂ gas) does not flow into the reaction chamber in the hydrogen plasma step.

However, in some other embodiments, it also supplies some form of nitrogen plasma, radicals, or nitrogen reactive species in the form of atomic nitrogen. Thus, in some embodiments, the second reactant has a compound having both N and H, such as _{NH 3} , N ₂ H _{4 , a mixture of N 2} / H ₂ , or an NH bond. Reactants formed from other precursors can be included. In some embodiments, the second reactant, at least in part, can be formed from N _2. In some embodiments, the second reactant, at least partially, be formed from _{H 2} and _{N 2,} and _{H 2} and _{N 2,} from about 100: 1 to about 1: 100, about 20: 1 to about 1:20, about 10: 1 to about 1:10, about 5: 1 to about 1: 5, and / or about 2: 1 to about 4: 1, and in some cases 1: 1. It is supplied at a flow rate ratio (H ₂ / N _2). For example, a hydrogen-containing plasma for depositing SiOC _{can be generated using both N 2} and H ₂ in one or more ratios described herein.

In some embodiments, the gas used to generate the reactive species, such as plasma, can consist essentially of argon or another noble gas. In some embodiments, the plasma output used to generate the hydrogen-containing plasma is about 5 watts (W) to about 5000 W, 10 W to about 2,000 W, about 50 W to about 1000 W, about 100 W to about 1000 W, or It can be about 100 W to about 500 W. In some embodiments, the plasma output used to generate the hydrogen-containing plasma can be from about 100 W to about 300 W. In some embodiments, the hydrogen-containing plasma can also include argon or another noble gas.

SiOC Membrane Properties In the SiOC thin films deposited by some of the embodiments described herein, the impurity level or concentration is less than about 3 atomic%, less than about 1 atomic%, less than about 0.5 atomic%, or about 0.1 atom. Can be less than%. For some thin films, the total impurity level, excluding hydrogen, can be less than about 5 atomic%, less than about 2 atomic%, less than about 1 atomic%, or less than about 0.2 atomic%. Further, in some thin films, the hydrogen level can be less than about 30 atomic%, less than about 20 atomic%, less than about 15 atomic% or less than about 10 atomic%. As used herein, impurities can be considered as any element other than Si, O and / or C. In some embodiments, the thin film does not contain argon.

In some embodiments, the deposited SiOC membrane does not contain a measurable amount of hydrogen. However, in some embodiments, a SiOC film containing hydrogen is deposited. In some embodiments, the deposited SiOC film comprises less than about 30 atomic%, less than about 20 atomic%, less than about 15 atomic%, less than about 10 atomic%, or less than about 5 atomic% hydrogen. In some embodiments, the thin film does not contain argon.

According to some embodiments, the SiOC thin film can exhibit a step coverage and pattern loading effect of greater than about 50%, greater than about 80%, greater than about 90%, or greater than about 95%. In some cases the step coverage and pattern loading effect can exceed about 98% and in other cases about 100% (within the accuracy of the measuring tool or method). In some embodiments, the step coverage and pattern loading effect can be greater than about 100%, greater than about 110%, greater than about 120%, greater than about 130%, or greater than about 140%. These values have an aspect ratio of 2 or more, an aspect ratio of about 3 or more in some embodiments, an aspect ratio of about 5 or more in some embodiments, and an aspect ratio of about 5 or more in some embodiments. It can be obtained in 8 or more shapes.

In some embodiments, the step coverage is about 50% to about 110%, about 80% to about 110%, about 90% to about 110%, about 95% to 110%, about 98% to 110%, Or it can be about 100% to 110%. In some embodiments, the step coverage is about 50% to about 100%, about 80% to about 100%, about 90% to about 100%, about 95% to 100%, or about 98% to 100%. Can be.

In some embodiments, the growth rate of the membrane is from about 0.01 Å / cycle to about 5 Å / cycle, from about 0.05 Å / cycle to about 2 Å / cycle. In some embodiments, the growth rate of the membrane exceeds about 0.05 Å / cycle, exceeds about 0.1 Å / cycle, exceeds about 0.15 Å / cycle, exceeds about 0.3 Å / cycle, and Exceeds about 0.3 Å / cycle and exceeds about 0.4 Å / cycle. As used herein, the "pattern loading effect" is used in its usual sense in the art. The pattern loading effect can be recognized with respect to impurity content, density, electrical properties and etch rate, but unless otherwise stated, the term pattern loading effect as used herein refers to the substrate on which the structure resides. Refers to the change in film thickness in the region. That is, the pattern loading effect can be shown as the film thickness on the side wall or bottom of the shape inside the three-dimensional structure with respect to the film thickness on the side wall or bottom of the three-dimensional structure / shape facing the open field. As used herein, a 100% pattern loading effect (or ratio 1) represents a nearly perfectly uniform membrane property of the entire substrate, regardless of shape, i.e., in other words, a pattern loading effect (shape vs. open field). There is no difference in specific film properties such as thickness).

In some embodiments, the SiOC film is deposited to a thickness of about 3 nm to about 50 nm, about 5 nm to about 30 nm, and about 5 nm to about 20 nm. These thicknesses can be obtained in shape sizes (widths) of less than about 100 nm, about 50 nm, less than about 30 nm, less than about 20 nm, and in some cases less than about 15 nm. According to some embodiments, the SiOC film is deposited on the three-dimensional structure and the thickness at the side walls can be slightly over 10 nm. In some embodiments, SiOC films larger than 50 nm can be deposited. In some embodiments, SiOC films larger than 100 nm can be deposited. In some embodiments, the SiOC film is deposited to a thickness greater than about 1 nm, greater than about 2 nm, greater than about 3 nm, greater than about 5 nm, and greater than about 10 nm.

According to some embodiments, SiOC films of various wet etch rates (WER) can be deposited. When using a blanket WR (nm / min) at 0.5 wt% dHF, the WER value of the SiOC film can be less than about 5, less than about 4, less than about 2 or less than about 1. In some embodiments, the WER value of the SiOC film can be significantly less than 1. In some embodiments, the WER value of the SiOC film can be less than about 0.3, less than about 0.2, or less than about 0.1. In some embodiments, the WER value of the SiOC film can be less than about 0.05, less than about 0.025, or less than about 0.02.

Comprehensive WER (nm / min) (WERR) at 0.5 wt% dHF relative to WER of the thermal oxide can be less than about 3, less than about 2, less than about 1 or less than about 0.5. In some embodiments, the comprehensive WR at 0.5 wt% dHF relative to the WR of TOX can be less than about 0.1.

In some embodiments where the PEALD process is performed at a temperature below about 100 ° C., the comprehensive WR (nm / min) at 0.5 wt% dHF relative to the WER of the thermal oxide is less than about 10, less than about 5. It can be less than about 3 and less than about 2 or less than about 1.

Further, in some embodiments, the fins, trenches, etc. are substantially perpendicular to the etching rate of the SiOC film deposited on a substantially horizontal surface such as the upper surface of the three-dimensional shape of the fins, trenches, etc. at 0.5 wt% dHF. The side wall etching rate of the SiOC film deposited on the three-dimensional shape, eg, the ratio of WER, is about 1 to about 2, about 2 to about 5, about 5 to about 10, about 10 to about 20, or, if any. Can be about 20 or more. In some embodiments, the ratio of the WER of the SiOC film deposited on the vertical surface of the three-dimensional shape to the WER of the SiOC film deposited on the upper surface of the three-dimensional shape is about 2 or more, about 5 or more, about 10 or more. It can be about 15 or more or about 20 or more.

In some embodiments, the WER of the SiOC film deposited on or in a nearly vertical surface of the three-dimensional shape, eg, a side wall surface, and a nearly horizontal surface of the three-dimensional shape, eg, on or in the top surface. The WER ratios of the SiOC films deposited in the above are about 1 to about 0.5, about 0.5 to about 0.2, about 0.2 to about 0.1, and about 0.1 to about 0.05. In some cases it can be less than about 0.05. In some embodiments, the ratio of the WER of the SiOC film deposited on the nearly vertical surface of the three-dimensional shape to the WER of the SiOC film deposited on the nearly horizontal surface of the three-dimensional shape is about 0.5 or less. It can be about 0.2 or less, about 0.1 or less, or about 0.05 or less.

In some embodiments, the ratio of the WER of the SiOC film deposited on or in the nearly vertical surface of the three-dimensional shape, eg, the side wall surface, to the WER of the TOX is about 5 to about 10, about 2 to 2. It can be about 5, about 1 to about 2, about 0.5 to about 1, or about 0.1 to about 0.5. In some embodiments, the ratio of the WER of the SiOC film deposited on or in the nearly vertical surface of the three-dimensional shape, eg, the side wall surface, to the WER of the TOX is about 0.1 or more, about 0. It can be 5 or more, about 1 or more, about 2 or more, about 5 or more, or about 10 or more.

In some embodiments, in SiOC formed by one or more of the processes described herein, the ratio of WER in a nearly vertical region to WER in a nearly horizontal region, eg, 0. At 5 wt% dHF, it can be about 1. For example, the wet etch rate of a SiOC thin film formed on a substantially vertical surface (for example, a side wall surface) of a three-dimensional structure on the substrate surface and the wet etch rate of a SiOC thin film formed on a substantially horizontal surface (for example, an upper surface). The ratio of can be the same or almost the same. In some embodiments, the ratio may be about 4 to about 0.5, about 2 to about 0.75, about 1.25 to about 0.8, or about 1.1 to about 0.9. can. These ratios can be obtained in shapes having an aspect ratio of about 2 or more, about 3 or more, about 5 or more, and further about 8 or more.

In some embodiments, the SiOC formed by one or more of the processes described herein advantageously has a horizontal and vertical region WERR of about 1 at, for example, 0.5 wt% dHF. Can be. For example, the wet etch rate of a SiOC thin film formed on the horizontal surface (eg, top surface) of a three-dimensional structure on the substrate surface and the wet etch rate of a SiOC thin film formed on a vertical surface (eg, side wall surface). The ratio with and can be the same or almost the same. In some embodiments, the ratio is about 0.25 to about 2, about 0.5 to about 1.5, about 0.75 to about 1.25, or about 0.9 to about 1.1. be able to. These ratios can be obtained in shapes having an aspect ratio of about 2 or more, about 3 or more, about 5 or more, and further about 8 or more.

In some embodiments, the amount of etching of the SiOC film according to the present disclosure is about one-half the amount of etching observed with _{thermal SiO 2 (TOX) in the 0.5 wt% HF immersion process.} It can be one-fifth, one-tenth or less (eg, in the process of removing TOX from about 2 to about 3 nm, when deposited by the methods disclosed herein, about Remove less than one-half, one-half, one-fifth, and one-tenth SiOC).

In some embodiments, SiOC films less than about 2 nm can be removed by a 0.5 wt% HF immersion process with an etching time of 5/5. In some embodiments, SiOC films less than about 2 nm can be removed by a 0.5 wt% HF immersion process with an etching time of 60 minutes.

In some embodiments, the amount of etching of the SiOC film according to the present disclosure is about one-half the amount of etching observed with _{thermal SiO 2 (TOX) in the 0.5 wt% HF immersion process.} It can be one-fifth, one-tenth or less (eg, in the process of removing TOX from about 2 to about 3 nm, when deposited by the methods disclosed herein, about Remove less than one-half, one-half, one-fifth, and one-tenth SiOC).

In some embodiments, SiOC films less than about 2 nm can be removed by a 0.5 wt% HF immersion process with an etching time of 5/5. In some embodiments, SiOC films less than about 2 nm can be removed by a 0.5 wt% HF immersion process with an etching time of 60 minutes.

All atomic percentage (ie,% atomic%) values described herein are for brevity and, as it is difficult to analyze hydrogen quantitatively and accurately, unless otherwise stated. Exclude hydrogen. However, in some embodiments, the hydrogen content of the membrane is less than about 20 atomic%, less than about 10 atomic%, or less than about 5 atomic% if hydrogen can be analyzed with reasonable accuracy. In some embodiments, the deposited SiOC thin film can contain up to about 70% oxygen on an atomic basis (atomic%). In some embodiments, the SiOC membrane can contain from about 10% to about 70%, about 15% to about 50%, or about 20% to about 40% oxygen on an atomic basis. In some embodiments, the SiOC membrane can contain at least about 20%, about 40% or about 50% oxygen on an atomic basis.

In some embodiments, the deposited SiOC thin film can contain up to about 40% carbon on an atomic basis (atomic%). In some embodiments, the SiOC film is about 0.1% to about 40%, about 0.5% to about 40%, about 1% to about 30%, or about 5% to about 20 on an atomic basis. Can contain% carbon. In some embodiments, the SiOC membrane can contain at least about 1%, about 10% or about 20% carbon on an atomic basis.

In some embodiments, the deposited SiOC thin film can contain up to about 50% silicon on an atomic basis (atomic%). In some embodiments, the SiOC film can contain from about 10% to about 50%, about 15% to about 40%, or about 20% to about 35% silicon on an atomic basis. In some embodiments, the SiOC film can contain at least about 15%, about 20%, about 25% or about 30% silicon on an atomic basis.

In some embodiments, the deposited SiOC thin film can contain up to about 40% sulfur on an atomic basis (atomic%). In some embodiments, the SiOC film is about 0.01% to about 40%, about 0.1% to about 40%, about 0.5% to about 30%, or about 1% to atomically. It can contain about 20% sulfur. In some embodiments, the SiOC membrane can contain at least about 1%, about 10% or about 20% sulfur on an atomic basis.

In some embodiments, the deposited SiOC membrane is free of measurable amounts of nitrogen. However, in some embodiments, a nitrogen-containing SiOC film is deposited. In some embodiments, the deposited SiOC film is less than about 30 atomic%, less than about 20 atomic%, less than about 15 atomic%, less than about 10 atomic%, less than about 5 atomic% nitrogen, less than about 1 atomic%. Nitrogen, or less than about 0.1 atomic% nitrogen. In some embodiments, the SiOC thin film is nitrogen free.

As mentioned above, in some embodiments, the SiOC film can include a Si—C bond and / or a Si—O bond. In some embodiments, the SiOC film can further include a Si—N bond. In some embodiments, the SiOC film can further comprise a Si—S bond. In some embodiments, the SiOC film can include Si—C and Si—O bonds and may not include Si—N bonds. In some embodiments, the SiOC film can include Si—N and Si—O bonds and may not include Si—C bonds. In some embodiments, the SiOC film can include Si—N and Si—C bonds and may not include Si—O bonds. In some embodiments, the SiOC film can include Si—S bonds, Si—C bonds and Si—O bonds and may not include Si—N bonds. In some embodiments, the SiOC film can include Si—S and Si—C bonds and may not include Si—O bonds. In some embodiments, the SiOC film can include Si—S and Si—O bonds and may not include Si—C bonds. In some embodiments, the SiOC membrane can contain more Si—O bonds than Si—C bonds, eg, a ratio of Si—O bonds to Si—C bonds of about 1: 1 to about. It can be 10: 1. In some embodiments, the deposited SiOC film can include one or more of SiN, SiO, SiC, SiCN, SiON, SiOSC, SiSC, SiOS and / or SiOC.

In some embodiments, the SiOC membrane is not a low-k membrane, for example, the SiOC membrane is not a porous membrane. In some embodiments, SiOC is a continuous membrane. In some embodiments, the SiOC film has a k value of less than about 10. In some embodiments, the SiOC film has a k value of less than about 7. In some embodiments, the SiOC film has a k value of about 2 to about 10. In some embodiments, the SiOC film has a k value of less than about 5.0, less than about 4.5, less than about 4.3, and less than about 4.1. In some embodiments, the SiOC film has a k value of about 3.0 to about 7, about 3.0 to about 5.5, about 3.0 to about 5.0, and about 3.5 to about 4. 8, about 3.5 to about 4.7. In some embodiments, the SiOC film has a higher k value than any low-k film. In some embodiments, the SiOC film has a higher _{k value than pure SiO 2.}

In some embodiments, the SiOC film deposited according to the present disclosure does not include a laminated or nano-laminated structure.

In some embodiments, the SiOC membrane deposited according to the present disclosure is not a self-assembled monolayer (SAM). In some embodiments, the SiOC membranes deposited according to the present disclosure do not consist of separate solid molecules that are not bound to each other. In some embodiments, the SiOC membrane deposited according to the present disclosure comprises a material that is substantially bonded or linked. In some embodiments, the SiOC film deposited according to the present disclosure is not a functional layer, has no amino functionality, and / or is not used as a functional surface. In some embodiments, the SiOC membrane deposited according to the present disclosure is not terminated with _{-NH 2 groups.} In some embodiments, the SiOC film deposited according to the present disclosure does not contain _{a large amount of -NH 2 groups.}

An exemplary SiOC thin film was deposited by the PEALD process described herein. BTESE was used as the silicon precursor and the bottle temperature was between 80 ° C and 110 ° C. Of H ₂ was used as the second reactant, and by applying a RF power of 200W to the second reactant to generate a plasma. One SiOC sample was deposited on the substrate or at a deposition temperature of 200 ° C., and another SiOC sample was deposited at a deposition temperature of 300 ° C.

For some SiOC samples, the precursor pulse time was 4 seconds, the precursor purge time was 4 seconds, the plasma pulse time was 4 seconds, and the plasma purge time was 0.5 seconds. In another sample, the precursor pulse time was 10 seconds, the precursor purge time was 4 seconds, the plasma pulse time was 4 seconds, and the plasma purge time was 0.5 seconds. In another sample, the precursor pulse time was 4 seconds, the precursor purge time was 10 seconds, the plasma pulse time was 4 seconds, and the plasma purge time was 0.5 seconds.

FIG. 3 shows the growth (Å / cycle) per cycle of the SiOC membrane deposited by the PEALD process described herein and the precursor bottle temperature. As shown in FIG. 3, the growth rate increased with the bottle temperature, and the sample deposited at the deposition temperature of 200 ° C. was higher than the sample deposited at the deposition temperature of 300 ° C. The growth rate was saturated at about 0.3 Å / cycle at a bottle temperature of 110 ° C. and a deposition temperature of 200 ° C.

FIG. 4 shows the plasma per cycle growth (Å / cycle), refractive index, and WERR of WERR in dHF (0.5 wt%) of SiOC films deposited by the PEALD process described herein. Shown as a function of output. BTESE was used as the silicon precursor and H ₂ was used as the second reactant. Plasma was generated by applying RF power of 200W to 800W to the second reactant. The deposition temperature was 200 ° C., the precursor pulse time was 4 seconds, the precursor purge time was 4 seconds, the plasma pulse time was 4 seconds, and the plasma purge time was 0.5 seconds.

As shown in FIG. 4, the growth rate of the SiOC film decreased as the plasma output increased. The index of refraction of the sedimentary film increased with increasing plasma output. It was found that the ratio of WER to TOX WER (WERR to TOX) of the deposited SiOC film decreased with increasing plasma output. That is, higher wet etch resistance was obtained with increasing plasma output, and the WERR with respect to TOX reached 0.2 at a plasma output of 800 W.

FIG. 5 shows the growth per cycle (Å / cycle) of the SiOC membrane deposited by the PEALD process described herein and the second reactant gas mixing ratio (N ₂ / (N ₂ + H ₂ )). .. BTESE was used as a silicon precursor and the deposition temperature was 200 ° C. The precursor pulse time for each cycle was 4 seconds, the precursor purge time was 4 seconds, the plasma pulse time was 4 seconds, and the plasma purge time was 0.5 seconds. The second reactant gas flow was 100 sccm and the Ar carrier gas was 600 sccm. The composition of the second reactant gas, respectively 3 SiOC samples consist essentially of H _2, a mixture of H ₂ and N _2, was changed consist essentially of N _2. A sample using only Ar carrier gas as the second reaction gas was also prepared. As shown in FIG. 5, the maximum growth rate (about 0.25 Å / cycle) was obtained using a second reactant gas _{essentially consisting of H 2 and an Ar carrier gas.} Low with a second reactant gas containing a mixture of H ₂ and N _2, a second reactant gas essentially _{consisting of N 2} and a second reactant gas essentially consisting of Ar carrier gas. Growth rate was observed. Therefore, although not bound by any one theory, _{it is considered that the addition of N2 to the second} reactant gas inhibits the growth of the SiOC membrane.

As used herein, the term "about" can refer to a value within 15%, within 10%, within 5%, or within 1% of a given value.

The terms "membrane" and "thin film" are used herein for brevity. "Membrane" and "thin film" shall mean any continuous or discontinuous structures and materials deposited by the methods disclosed herein. For example, "film" and "thin film" are 2D materials, nanorods, nanotubes, or nanoparticles, as well as a single partial or complete molecular layer, or partial or complete atomic layer, or atoms and / or molecules. Can include clusters of. The "film" and "thin film" may include a material or layer that contains pinholes but is at least partially continuous.

Those skilled in the art should appreciate that a number of diverse modifications can be made without departing from the spirit of the invention. The shapes, structures, properties and precursors described can be combined in any suitable manner. Therefore, it should be clearly understood that the embodiments of the invention are for illustration purposes only and are not intended to limit the scope of the invention. All modifications and modifications shall be within the scope of the invention as defined by the appended claims.

Claims (20)

A method of forming a silicon oxycarbide (SiOC) thin film on a substrate by a plasma enhanced atomic layer deposition (PEALD) process in a reaction space.
The step of bringing the surface of the substrate into contact with the nitrogen-free vapor phase silicon precursor,
Here, the vapor phase silicon precursor contains bis (triethoxysilyl) ethane (BTESE) or 3-methoxypropyltrimethoxysilane (MPTMS).
A step of bringing the surface of the substrate into contact with at least one reaction species generated by plasma formed from a second reaction product containing hydrogen, wherein the second reaction product does not contain oxygen.
A method comprising at least one deposition cycle comprising optionally repeating the contacting step until a SiOC film of a desired thickness is formed. The method according to claim 1, wherein the ratio of the wet etch rate of the SiOC thin film to the wet etch rate of the thermal silicon oxide is less than 5. The method of claim 1, wherein the SiOC thin film is deposited on a three-dimensional structure on the substrate. The wet etch rate ratio between the wet etch rate of SiOC formed on the vertical surface of the three-dimensional structure and the wet etch rate of the SiOC formed on the horizontal surface of the three-dimensional structure is 0.5% by weight diluted HF. The method according to claim 3, wherein the ratio is 1:20 to 20: 1. The method of claim 1, wherein the reaction species comprises a hydrogen plasma, a hydrogen atom, a hydrogen radical or a hydrogen ion. The method of claim 5, wherein the second reactant _{comprises H 2.} The method of claim 1, wherein the reaction species is produced from a second reactant comprising a noble gas. The method of claim 1, wherein the reaction species is produced from a second reactant comprising less than 20 atomic% nitrogen. The method of claim 1, wherein the SiOC thin film contains at least 20 atomic% oxygen. The method of claim 1, wherein the SiOC thin film contains at least 0.1 atomic% carbon. The method of claim 1, wherein the SiOC thin film contains less than 10 atomic% nitrogen. A method of forming a silicon oxycarbide (SiOC) thin film on a substrate in a reaction space comprising multiple deposition cycles, wherein at least one deposition cycle is performed.
It comprises the step of alternately and sequentially contacting the surface of the substrate with a second reactant comprising a nitrogen-free silicon precursor and at least one reactive species containing hydrogen.
The deposition cycle is repeated two or more times to form the SiOC thin film, and the silicon precursor contains bis (triethoxysilyl) ethane (BTESE) or 3-methoxypropyltrimethoxysilane (MPTMS).
Method. 12. The method of claim 12, wherein the at least one reactive species is generated by a plasma formed from an oxygen-free gas. 12. The method of claim 12, wherein the at least one reactive species is generated by a plasma formed from a nitrogen-free gas. 12. The method of claim 12, wherein at least one deposition cycle is a plasma enhanced atomic layer deposition (PEALD) cycle. 15. The method of claim 15, wherein the reaction species is generated by applying an RF power of 5 watts (W) to 5000 W to the second reactant. 12. The method of claim 12, wherein the deposition cycle is carried out at a process temperature of 100 ° C to 300 ° C. 12. The method of claim 12, wherein the deposition cycle is carried out at a process temperature of less than 100 ° C. 12. The method of claim 12, wherein the substrate comprises an organic material. A method of depositing a silicon oxycarbide (SiOC) thin film on a substrate in a reaction space.
Contacting the surface of the substrate to a silicon precursor that does not contain nitrogen, wherein said silicon precursor comprises a bis (triethoxysilyl) ethane (BTESE) or 3-methoxypropyl trimethoxy silane (MPTMS),
A step of exposing the substrate to purge gas and / or vacuum to remove excess silicon precursors and reaction by-products, if any.
A step of bringing the surface of the substrate into contact with a second reactant containing hydrogen, wherein the second reactant comprises at least one reactant produced by plasma.
A step of exposing the substrate to purge gas and / or vacuum to remove excess second reactants and reaction by-products, if any.
A method comprising repeating the contacting step until a SiOC thin film of a desired thickness is formed.

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